Process for the preparation of 4-halogen-para-phenyl-ortho-benzoyl-benzoic acid



Patented Dec. 30, 1930 PHILIP H. GROGGINS, OF WASHINGTON, DISTRICT OFCOLUMBIA rnocnss son THE 1?.REPAR-ATION No Drawing.

QIF 4-HALOGEN-PARA-PHENYL-ORTHOBENZOYL- BENZOIG ACID Application filedAugust 8, 1929. Serial 1T0. 384,506.

(GRANTED UNDER THE ACT OF MARCH 3, 1883, AS AMENDED APRIL 30, 1928; 370O. G. 757) i num base by hydrolysis.

I have found that -halogen-diphenyl can be condensed with phthalicanhydride in the presence of a suitable condensing agent such asanhydrous aluminum chloride or ferric chloride to give the aluminum oriron base of %-halogen-para-phenyl-ortho-benzoyl-benzoic acid. I preferto use anhydrous aluminum chloride for the reason that it provides themeans of obtaining a smooth reaction, a

-' product of high purity, and a yield not far from the theoretical. Thereactions involved in the preparation of the intermediate anhydrousaluminum base, and the keto acid which is obtained upon hydrolysis ofthe aluminum compound are probably best expressed by the following twoequations where hlg represents a halogen substituent such as chlorine orbromine:

O 7 l 4 111g 0 1 +A1Gl; -HC17| o H o i 0 0 w A1013 0 -tl O-Mg O a) (fenWhen -chloro-diphenyl is condensed in the above manner, the greenanhydrous aluminum base of 4L-chloro-para-phenyl-orthobenZoyl-benzoicacid is obtained. Upon hydrolysis this yields4-chloro-para-phenyl-ortho-benzoyl-benzoic acid, which is a whitecrystalline solid, practically insoluble in hot Water. It is readilysoluble in alcohol, chlorobenzen-e and glacial acetic acid. 'When thesodium or ammonium salts are made by treating with alkaline orammoniacal solutions,

these are readily soluble in cold water.

Crude 4-chloro-para-phenyl-ortho benzoylbenzoic acid melts at 249.0" C.lVhen re crystallized from toluene or glacial acetic acid the meltingpoint is 24913-2506 C.

The preparation of the aluminum base of 4-halogen-para phenyl-orthobenzoyl benzoic acid is best made using molecular proportions ofphthalic anhydride and ls-halogen-diphenyl. As in the preparation ofparaphenyl-ortho-benzoyl-benzoic acid described in my copendingapplication Serial No. 384,505, dated August 8, 1929, it is notnecessary to use inert solvents such as carbon disulfide or aromaticnitro-compounds to carry out the react-ion.

Without limiting my invention to any particular procedure the followingexamples illustrate my preferred methods of preparation:

Ewample l.-On-e hundred forty eight parts of phthalic anhydride, 188.5partsof dry 4-choloro-diphenyl, and 293 parts of anhydrous aluminumchloride are put into a mill and thoroughly agitated for two hours. Thehydrogen chloride which is liberated even at room temperature is drawnoh by suitable connections. Heat is applied and the temperature keptfrom 10 C. to 120 C, until the evolution of hydrogen chloride iscompleted. The mixing of the ingredients is continued until the batchcools to room temperature and the aluminum base is obtained as ananyhdrous green powder. To obtaind-chloro-para-phenyl-ortho-benzoylbenzoic acid, the aluminum base isslowly added to 2000 parts of iced 10 per cent sulfuric acid underagitation. An almost colorless, crystalline, crude, product is obtained.

Emample I[.One hundred forty-eight parts of phthalic anhydride, 188.5parts of l-chloro-diphenyl, and 293 parts of anhydrous aluminum chlorideare put into an agitated vessel. Five hundred parts of carbon disulfideare then slowly added. After Warming on the steam bath until theevolution of hydrogen chloride has ceased the carbon disullide isremoved and the remaining aluminum base oft-chloro-para-phenylortho-benzoyl-benzoic acid is obtained. This may behydrolyzed to obtain the keto acid or may be used in the preparation ofe -chlorobeta-p11enyl-anthraquinone.

Iiwamplc [[[.The preparation of a;- bromo-para-phenyl ortho benzoylbenzoic acid may be carried out following the pre cedures in Examples Iand II, except that molecular proportion of l-bromo-diphenyl areemployed in place of the corresponding chloro derivative.

I am aware that numerous changes may be made, and many details of theprocess varied through a wide range without departing from theprinciplesof this invention, and I therefore do not purpose limiting the patentranted hereon, otherwise than necessitated by the prior art.

I claim as my invention- 1. A process for preparing t-halogenderivatives of para-phenyl-ortho-benzoyl-benzoic acid which comprisescondensing d-halogendiphenyl with phthalic anhydride.

2. A process for preparing the aluminum base of bhalogen derivatives ofpara-phenylortho-benzoyl-bcnzoic acid which comprises condensingsthalogen-diphenyl with pht-halic anhydride in the resence of aluminumchloride.

3. A process of preparing the aluminum base ofie-ch]oro-para-phenyl-ortho-benzoylbenzoic acid which comprisescondensing approximately molecular proportions of 4:- chloro-diphenyland phthalic anhydride in the presence of anyhdrous aluminum ehoride asa condensing agent.

4. A process of preparing it-chlormparaphenyl-ortho-benzoyl-benzoic acidwhich comprises condensing 4-chlorodiphenyl with phthalic anhydride inthe presence of anhydrous aluminum chloride and then hydrolyzing thealuminum intermediate base that is obtained.

5. A process of preparing the aluminum base of-chloro-para-phenyl-ortho-benzoylbenzoic acid which comprises condensing4- chlorodiphenyl with phthalic anhydride in the presence of anhydrousaluminum chloride; the reaction taking place in the presence of an inertsolvent.

6. As a new article of manufacture the aluminum base of4:-chloro-para-phenylortho-benzoyl-benzoic acid having the followingformula:

7 As anew article of manufacture4-chloropara-phenyl-ortho-benzoyhbenzoio acid having most probably thefollowing chemical formula o ti- @471 4 C {J ()//\OH PHILIP H.GROG-GINS.

